CN112920369B - Self-antibacterial lactic acid-based waterborne polyurethane, preparation method and emulsion thereof - Google Patents
Self-antibacterial lactic acid-based waterborne polyurethane, preparation method and emulsion thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of functional polymer materials, and particularly relates to self-antibacterial lactic acid-based waterborne polyurethane, a preparation method thereof and emulsion thereof. According to the invention, the self-antibacterial lactic acid-based waterborne polyurethane is introduced with the waterborne chitosan and hinokitiol structures on the side chain of the large polyurethane long chain and is uniformly distributed, so that two substances with different antibacterial and biocidal mechanisms generate a synergistic effect of biocidal and antibacterial effects mutually, the drug resistance of bacterial organisms can be effectively reduced, and meanwhile, the two substances are grafted on the polyurethane long chain in a chemical bond manner, so that the antibacterial effect is lasting.
Description
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to self-antibacterial lactic acid-based waterborne polyurethane, a preparation method thereof and emulsion thereof.
Background
The waterborne polyurethane is a novel high-molecular synthetic material taking water as a dispersion medium instead of an organic solvent, has the advantages of no pollution, safety, reliability, excellent mechanical property, good compatibility, easy modification and the like, and is widely applied to the fields of leather making, textiles, coatings, printing, building industry, adhesives and the like.
The chitosan is a product of natural polysaccharide chitin after partial acetyl is removed, has abundant resources, is a recyclable renewable resource, and has good biodegradability, biocompatibility, nontoxicity, bacteriostasis and the like. Chitosan is insoluble in water and common organic solvents, so the chitosan is rarely applied to water-based polyurethane, but the structure of the chitosan has a large number of amino groups and hydroxyl groups, the chitosan can be subjected to various chemical reactions (acylation, alkylation, etherification, esterification, quaternization, oxidation, grafting, crosslinking and the like), and various derivatives are generated after chemical modification, the water solubility of the chitosan can be greatly improved, and the antibacterial property of the chitosan is even stronger than that of the chitosan.
The hinokitiol is a monoterpene natural compound with tropolone skeleton extracted from the trunk of Chinese Taiwan cypress by Anderson in 1948, has good antibacterial property, and can kill bacteria and microbe in air and inhibit pathogenic bacteria of human.
In the prior art relating to the research on antibacterial aqueous polyurethane, the antibacterial property is generally achieved by physical and chemical methods. The physical method is to add a micromolecular antibacterial agent with antibacterial function in the synthesis process of polyurethane emulsion, and obtain the antibacterial waterborne polyurethane in a physical blending mode, wherein the antibacterial performance of the antibacterial waterborne polyurethane is not long enough, and the antibacterial effect is gradually reduced along with the prolonging of the service time. The chemical method is the mainstream of the current research, and the antibacterial agent is bonded into the polyurethane long chain by a chemical reaction bond method to achieve the long-term antibacterial effect.
According to the patent CN109694483A, quaternary ammonium salt with a long alkyl chain is introduced, and the number of carbon atoms in the long alkyl chain is controlled to be 1-12, so that the antibacterial performance of the coating can be effectively improved, and the aim of contact type antibacterial is fulfilled. However, the toxicity of the quaternary ammonium salt with a long alkyl chain is reduced along with the increase of the chain, when the number of carbon atoms in the alkyl chain is more than 16 or less than 10, the antibacterial effect is very small, the antibacterial capability is maximized only when the number of carbon atoms is 14, the bacteria can generate drug resistance after long-term use of the quaternary ammonium salt antibacterial agent, and the decomposed product has certain toxicity and is unfavorable for the environment. Patent CN109575235A discloses an antibacterial agent PHMG modified waterborne polyurethane, however, since PHMG is bonded into the main chain of polyurethane, positive charges cannot be ionized, and thus the PHMG can be adsorbed on the surface of negatively charged microorganisms, which hinders the action of lysozyme in cells, and destroys the surface structure of cells to achieve the antibacterial effect. Patent CN107652663A provides a preparation method of an antibacterial modified polyurethane material, which utilizes a salt formation mode of acidifying chitin with formic acid to connect chitin to the end of polyurethane, so as to form a good antibacterial effect. Patent CN107236109B uses citric acid to modify chitosan, and reasonably designs the modified chitosan molecules into the structure of the waterborne polyurethane, and combines the advantages of the mechanical properties of the waterborne polyurethane and the biodegradability of chitosan to synthesize a waterborne polyurethane containing chitosan structure, however, the waterborne polyurethane does not mention the antibacterial effect.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides self-antibacterial lactic acid-based waterborne polyurethane, a preparation method thereof and an emulsion thereof. The self-antibacterial lactic acid-based waterborne polyurethane emulsion refers to the condition that a high polymer side chain of the emulsion is connected with two antibacterial functional groups, namely water-soluble chitosan and hinokitiol, the water-soluble chitosan on the high polymer side chain of the antibacterial polyether polyurethane has the effect of killing microbes and resisting bacteria, and the hinokitiol on the high polymer side chain of the emulsion also has the effect of resisting bacteria and sterilizing, so that the self-antibacterial effect of the lactic acid-based waterborne polyurethane is achieved.
The technical scheme provided by the invention is as follows:
a self-antibacterial lactic acid-based waterborne polyurethane has the following structural general formula:
wherein:
degree of polymerization n 1 1 to 20;
degree of polymerization n 2 1 to 15;
general formula of X
To a degree of polymerization n thereof 3 1 to 15;
r is 2, 4-tolyl, 4' -diphenylmethyl, 3-methylene-3, 5, 5-trimethylcyclohexyl and 1, 6-hexylene;
p is 1, 2-diether-3-propyl, 1, 5-diether-3-amyl alkyl and 1, 4-diether-2-butyl.
According to the self-antibacterial lactic acid-based waterborne polyurethane provided by the technical scheme, the high-molecular side chain of the self-antibacterial lactic acid-based waterborne polyurethane is connected with two antibacterial functional groups, namely water-soluble chitosan and hinokitiol, the water-soluble chitosan on the high-molecular side chain of the antibacterial polyether polyurethane has the biocidal and antibacterial effects, and the hinokitiol on the high-molecular side chain of the self-antibacterial lactic acid-based waterborne polyurethane also has the antibacterial and sterilization effects, so that the self-antibacterial effect of the lactic acid-based waterborne polyurethane is achieved.
The invention also provides a preparation method of the self-antibacterial lactic acid-based waterborne polyurethane, which comprises the following steps:
1) dissolving chitosan in an aprotic solvent containing 0.3-0.7 wt% of acetic acid, dissolving and clarifying, adding a saccharide compound, stirring at room temperature for reacting for 4-6 h, adding a reducing agent for continuing to react for 24-48 h, filtering out solids after the reaction is finished, washing with MeOH, and drying the solids to obtain water-soluble chitosan;
2) adding acetone, diisocyanate compound, lactic acid based polyol and tin catalyst into a reactor, and reacting under N 2 Stirring and reacting for 1.5-2 h in an oil bath system at the temperature of 65-70 ℃, then adding a chain extender to continue reacting for 2-4h, and then according to the mass ratio of-OH added to-NCO in the system of 1 (1) ((1))5-2.5) adding hinokitiol for end capping, and reacting at 75-80 ℃ for 0.5-1 h to obtain a partially end-capped aqueous polyurethane prepolymer; the adding amount of the acetone is 1 to 10 weight percent of the system;
3) adding the water-soluble chitosan obtained in the step 1) into the partially end-capped aqueous polyurethane prepolymer obtained in the step 2) for several times, simultaneously heating to 80-85 ℃ for reaction for 3-5 hours, supplementing acetone in the reaction process to control the viscosity of the system, controlling the viscosity to be 1-500CP, reducing the temperature to 40-45 ℃ after the reaction is finished, slowly adding a certain amount of deionized water under high-speed stirring to emulsify and disperse the system, and finally carrying out reduced pressure distillation to remove the acetone, thus obtaining the self-antibacterial lactic acid-based aqueous polyurethane, wherein the solid content is controlled to be 20-40 wt%, and the viscosity is 1-200 CP;
wherein:
in the step 1), the molar use ratio of the chitosan, the saccharide compound and the reducing agent is (1.5-2): 1: (2-5);
in the step 2), the use amount ratio of the diisocyanate compound, the lactic acid-based polyol and the chain extender is (1-15): 1: (0.5-3), wherein the tin catalyst accounts for 0.5-0.7 wt% of the total mass of the three components;
in the step 3), the weight ratio of the water-soluble chitosan to the partially end-capped aqueous polyurethane prepolymer is (0-1): 1.
based on the technical scheme, the self-antibacterial lactic acid-based waterborne polyurethane can be prepared.
The principle of the above synthesis is as follows:
specifically, in the step 2), acetone, diisocyanate compound, lactic acid based polyol and tin catalyst are added into a reactor, and N is added 2 And (3) carrying out stirring reaction for 1.5-2 h in an oil bath system at the temperature of 65-70 ℃ under protection until theoretical NCO is reached, then adding a chain extender to continue the reaction for 2-4h, and adding a proper amount of acetone to reduce viscosity according to the viscosity condition of the system. And finally, according to the mass ratio of-OH to-NCO in the system of 1:2, adding hinokitiol for end capping, and reacting at 75-80 ℃ for 0.5-1 h to obtain the partially end-capped waterborne polyurethane prepolymer.
Specifically, in the step 3), the prepared water-soluble chitosan is added into the reaction system in the step 2) in a small amount for multiple times, the temperature is increased to 80-85 ℃ for reaction for 3-5 hours, acetone is added in the reaction process to control the viscosity of the system, after the reaction is finished, the temperature is reduced to 40-45 ℃, then a certain amount of deionized water is slowly added under high-speed stirring to emulsify and disperse the system, and finally, the acetone is removed through reduced pressure distillation to obtain the self-antibacterial lactic acid-based waterborne polyurethane emulsion.
Specifically, the carbohydrate is selected from any one or combination of more of lactose, maltose or D-ribose.
Specifically, the aprotic solvent is selected from any one or more of DCM, THF or MeCN.
Specifically, the reducing agent is selected from any one of sodium borohydride, sodium cyanoborohydride, or sodium triacetoxyborohydride.
Specifically, the diisocyanate compound is selected from any one or a combination of more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
Specifically, the general formula of the lactic acid-based polyol is shown as
Specifically, the chain extender is selected from any one or more of 1, 2-dihydroxy-3-propane sodium sulfonate (DHPA), 1, 5-dihydroxy-3-pentane sodium sulfonate, 1, 4-Butanediol (BDO) or 1, 4-dihydroxy-2-butane sodium sulfonate.
Specifically, the tin catalyst is selected from stannous octoate, dibutyltin dilaurate, dibutyltin bis (dodecyl sulfur), dibutyltin diacetate or stannous chloride.
The invention also provides a self-antibacterial lactic acid-based waterborne polyurethane emulsion which is formed by the self-antibacterial lactic acid-based waterborne polyurethane, has the solid content of 20-40 wt%, and is preferably formed by water.
The self-antibacterial lactic acid-based waterborne polyurethane emulsion provided by the technical scheme has remarkable antibacterial performance.
The beneficial effects of the invention are mainly embodied in the following aspects:
1. the raw materials of polylactic acid, chitosan, juniperitol and the like belong to biomass resources, and are green and environment-friendly.
2. The chitosan is obtained by modifying the carbohydrate, has very good hydrophilicity, and solves the problem of uniform dispersion of the chitosan in the synthetic waterborne polyurethane emulsion.
3. The chain extender provided by the invention is mainly sulfonic acid type, has stronger hydrophilicity than carboxylic acid type, higher ionization degree, better thermal stability, simpler synthesis process and no need of neutralization, and the obtained emulsion has very good dispersibility, water resistance, heat resistance and stability.
4. The water-based chitosan and the hinokitiol on the macromolecular side chain of the self-antibacterial lactic acid-based water-based polyurethane disclosed by the invention are uniformly distributed, two substances with different antibacterial and biocidal mechanisms generate a biocidal and antibacterial synergistic effect mutually, so that the drug resistance of bacteria organisms can be effectively reduced, and the two substances are grafted on a polyurethane long chain in a chemical bond manner, so that the antibacterial property is durable.
Drawings
FIG. 1 is an infrared spectrum of example 2 of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
Preparation of self-antibacterial lactic acid-based waterborne polyurethane emulsion Chitosan-lactone-BT-PU
Step one, preparation of Chitosan-lactone
Weighing 17.52g of chitosan, dissolving in DCM solvent containing 0.5% acetic acid, dissolving, clarifying, adding 51.34g of lactose, stirring at room temperature for reaction for 6h, and adding 6.59gNaBH 3 CN continues to react for 48h, after the reaction is finished, the solid is filtered, washed by MeOH and dried, and finally the water-soluble Chitosan Chitosan-lactone is obtained. The specific synthetic route is as follows:
step two, preparation of BT-PU
Weighing 20.88g of lactic acid-based polyol (hydroxyl value is 53.72mgKOH/g) in a reaction bottle, heating to 100 ℃, carrying out vacuum dehydration for 45min, then cooling to 70 ℃, adding 0.014g of stannous octoate, slowly dropwise adding 11.99g of diphenylmethane diisocyanate, reacting for 2h under the temperature condition after dropwise adding until theoretical NCO is reached, then adding 0.49g of 1, 4-butanediol and 1.56g of 1, 2-dihydroxy-3-propanesulfonic acid sodium salt, continuing to react for 4h, adding a proper amount of acetone in the reaction process to reduce viscosity, after the reaction reaches the theoretical NCO, finally adding 1.31g of hinokitiol for end capping, and keeping at 80 ℃ for reacting for 1h to obtain the partially capped waterborne polyurethane BT-PU prepolymer.
Step three, preparing Chitosan-lactone-BT-PU
Weighing 1.57g of the water-soluble Chitosan-lactone prepared in the first step, adding the water-soluble Chitosan-lactone into the reaction system in the second step for a plurality of times in a small amount, simultaneously keeping the temperature at 85 ℃ for reaction for 5 hours, supplementing acetone in the reaction process to control the viscosity of the system, reducing the temperature to 45 ℃ after the reaction is finished, slowly adding a certain amount of deionized water under high-speed stirring to emulsify and disperse the system, and finally carrying out reduced pressure distillation to remove the acetone to obtain the self-antibacterial lactic acid-based aqueous polyurethane emulsion Chitosan-lactone-BT-PU.
Example 2 preparation of self-antibacterial lactic acid-based aqueous polyurethane emulsion Chitosan-maltose-BT-PU
Step one, preparation of Chitosan-maltose
Weighing 17.52g of chitosan, dissolving the chitosan in THF solvent containing 0.5% acetic acid, adding 51.34g of maltose after the chitosan is dissolved and clarified, stirring the mixture at room temperature for reacting for 6 hours, and then adding 3.97g of NaBH 4 The reaction is continued for 48h, after the reaction is finished, the solid is filtered out, washed by MeOH and driedAnd finally obtaining the water-soluble Chitosan Chitosan-maltose. The specific synthetic route is as follows:
step two, preparation of BT-PU
Weighing 20.46g of lactic acid-based polyol (hydroxyl value is 54.83mgKOH/g) in a reaction bottle, heating to 100 ℃, carrying out vacuum dehydration for 45min, then cooling to 70 ℃, adding 0.014g of dibutyltin dilaurate, slowly dropwise adding 8.06g of hexamethylene diisocyanate, reacting for 2h under the temperature condition after dropwise adding until theoretical NCO is reached, then adding 0.49g of 1, 4-butanediol and 1.56g of 1, 2-dihydroxy-3-propanesulfonic acid sodium salt, continuing to react for 4h, adding a proper amount of acetone in the reaction process to reduce viscosity, after the reaction reaches the theoretical NCO, finally adding 1.31g of hinokitiol for end capping, and keeping at 80 ℃ for reacting for 1h to obtain the partially-capped waterborne polyurethane prepolymer BT-PU.
Step three, preparing Chitosan-maltose-BT-PU
Weighing 1.57g of the water-soluble Chitosan Chitosan-maltose prepared in the first step, adding the water-soluble Chitosan Chitosan-maltose into the reaction system in the second step for a plurality of times in a small amount, simultaneously keeping the temperature at 85 ℃ for reaction for 5 hours, supplementing acetone in the reaction process to control the viscosity of the system, reducing the temperature to 45 ℃ after the reaction is finished, slowly adding a certain amount of deionized water under high-speed stirring to emulsify and disperse the system, and finally carrying out reduced pressure distillation to remove the acetone to obtain the self-antibacterial lactic acid-based aqueous polyurethane emulsion Chitosan-maltose-BT-PU.
The infrared spectrum is 3321cm as shown in figure 1 -1 The peak of the N-H stretching vibration appeared to be 1687cm -1 The characteristic absorption peak of C ═ O stretching vibration (amide I band) in the amide appears, 1536cm -1 The characteristic absorption peak of the bending vibration of sigma N-H (amide II band), 1261cm -1 Characteristic absorption peaks of a C-N absorption band (amide III band) are shown, and the characteristic absorption peaks indicate that the antibacterial polyurethane has a urethane group structure; 2940cm -1 is-CH 3 Vibration peak of stretching of (2), 1720cm -1 A very small carbonyl stretch characteristic of the aromatic ketone appearsAbsorption peak at 1644cm -1 A very small stretching vibration peak of a C ═ C double bond appears, 1366cm -1 Is a delta CH vibration characteristic peak in tertiary carbon, 870cm -1 The outer bending vibration peak of C-H in C ═ C double bond indicates that the hinokitiol structure has been connected to the antibacterial polyurethane long chain; 1094cm -1 An ether bond-C-O-C stretching vibration characteristic absorption peak proves that the antibacterial polyurethane has a chitosan structure; 2859cm -1 is-CH 2 -peak of stretching vibration, 1758cm -1 Is the characteristic absorption peak of C ═ O stretching vibration in ester group, 1453cm -1 Is CH 3 Asymmetric deformation and CH 2 Peak of deformation vibration absorption at 1184cm -1 Is the absorption peak of the C-O-C stretching vibration characteristic in the ester group.
Example 3 preparation of self-antibacterial lactic acid-based aqueous polyurethane emulsion Chitosan-D-ribose-BT-PU
Step one, preparation of Chitosan-D-ribose
Weighing 17.52g chitosan, dissolving in MeCN solvent containing 0.5% acetic acid, adding 22.51g D-ribose after dissolving and clarifying, stirring at room temperature for reaction for 6h, then adding 22.22g NaB (OAc) 3 And H, continuously reacting for 48 hours, filtering out solids after the reaction is finished, washing with MeOH, and drying to finally obtain the water-soluble Chitosan Chitosan-D-ribose. The specific synthetic route is as follows:
step two, preparation of BT-PU
Weighing 19.90g of lactic acid-based polyol (hydroxyl value is 56.38mgKOH/g) in a reaction bottle, heating to 100 ℃, carrying out vacuum dehydration for 45min, then cooling to 70 ℃, adding 0.014g of dibutyltin bis (dodecyl sulfur) and slowly dropwise adding 10.65g of isophorone diisocyanate, reacting for 2h under the temperature condition after dropwise adding until theoretical NCO is reached, then adding 0.49g of 1, 4-butanediol and 1.71g of 1, 4-dihydroxy-2-butane sodium sulfonate, continuing to react for 4h, adding a proper amount of acetone in the reaction process to reduce viscosity, after the reaction reaches the theoretical NCO, finally adding 1.31g of hinokitiol to carry out end capping, and keeping at 80 ℃ for reaction for 1h to obtain the partially end-capped waterborne polyurethane BT-PU.
Step three, preparing Chitosan-D-ribose-BT-PU
Weighing 0.68g of the water-soluble Chitosan Chitosan-lactone prepared in the first step, adding the water-soluble Chitosan Chitosan-lactone into the reaction system in the second step for a plurality of times in a small amount, simultaneously keeping the temperature at 85 ℃ for reaction for 5 hours, supplementing acetone in the reaction process to control the viscosity of the system, reducing the temperature to 45 ℃ after the reaction is finished, slowly adding a certain amount of deionized water under high-speed stirring to emulsify and disperse the system, and finally carrying out reduced pressure distillation to remove the acetone to obtain the self-antibacterial lactic acid-based waterborne polyurethane emulsion Chitosan-D-ribose-BT-PU.
Example 4 preparation of self-antibacterial lactic acid-based aqueous polyurethane emulsion Chitosan-lactone-PU
Step one, preparation of Chitosan-lactone
Weighing 17.52g of chitosan, dissolving in DCM solvent containing 0.5% acetic acid, dissolving, clarifying, adding 51.34g of lactose, stirring at room temperature for reaction for 6h, and then adding 6.59g of NaBH 3 CN continuously reacts for 48 hours, after the reaction is finished, the solid is filtered out, then MeOH is used for washing, and drying is carried out, thus finally obtaining the water-soluble Chitosan Chitosan-lactone.
Step two, preparation of PU prepolymer
Weighing 20.34g of lactic acid-based polyol (hydroxyl value is 55.14mgKOH/g) in a reaction bottle, heating to 100 ℃, carrying out vacuum dehydration for 45min, then cooling to 70 ℃, adding 0.014g of stannous octoate, slowly dropwise adding 11.99g of diphenylmethane diisocyanate, reacting for 2h at the temperature until theoretical NCO is reached, then adding 0.49g of 1, 4-butanediol and 1.87g of 1, 5-dihydroxy-3-pentane sodium sulfonate, continuing to react for 4h, adding a proper amount of acetone in the reaction process to reduce viscosity, and finally obtaining the partially blocked waterborne polyurethane PU prepolymer.
Step three, preparing Chitosan-lactone-PU
Weighing 3.14g of the water-soluble Chitosan Chitosan-lactone prepared in the first step, adding the water-soluble Chitosan Chitosan-lactone into the reaction system in the second step for a plurality of times in a small amount, simultaneously keeping the temperature at 85 ℃ for reaction for 5 hours, supplementing acetone in the reaction process to control the viscosity of the system, reducing the temperature to 45 ℃ after the reaction is finished, slowly adding a certain amount of deionized water under high-speed stirring to emulsify and disperse the system, and finally carrying out reduced pressure distillation to remove the acetone to obtain the self-antibacterial lactic acid-based waterborne polyurethane emulsion Chitosan-lactone-PU.
Example 5 preparation of self-antibacterial lactic acid-based aqueous polyurethane emulsion BT-PU
Weighing 19.56g of lactic acid-based polyol (hydroxyl value is 57.35mgKOH/g) in a reaction bottle, heating to 100 ℃, carrying out vacuum dehydration for 45min, then the temperature is reduced to 70 ℃, 0.014g of dibutyltin dilaurate is added and slowly dropwise added, 8.06g of hexamethylene diisocyanate is reacted for 2h under the temperature condition after the dropwise addition is finished until theoretical NCO is reached, then 0.49g of 1, 4-butanediol and 1.56g of 1, 2-dihydroxy-3-sodium propanesulfonate are added for continuous reaction for 4 hours, a proper amount of acetone is added during the reaction process for viscosity reduction, after the reaction reaches the theoretical NCO, finally adding 2.62g of hinokitiol for end capping, keeping the temperature at 80 ℃ for reacting for 3h, cooling to 45 ℃ after the reaction is finished, and slowly adding a certain amount of deionized water under high-speed stirring to emulsify and disperse the system, and finally carrying out reduced pressure distillation to remove acetone to obtain the self-antibacterial lactic acid-based waterborne polyurethane emulsion BT-PU.
Example 6 preparation of self-antibacterial lactic acid-based aqueous polyurethane emulsion Chitosan-D-ribose-BT-PU
Step one, preparation of Chitosan-D-ribose
Weighing 17.52g chitosan, dissolving in MeCN solvent containing 0.5% acetic acid, adding 22.51g D-ribose after dissolving and clarifying, stirring and reacting for 6h at room temperature, then adding 22.22g NaB (OAc) 3 And H, continuously reacting for 48 hours, filtering out solids after the reaction is finished, washing with MeOH, and drying to finally obtain the water-soluble Chitosan Chitosan-D-ribose.
Step two, preparation of BT-PU
Weighing 20.12g of lactic acid-based polyol (hydroxyl value is 55.76mgKOH/g) in a reaction bottle, heating to 100 ℃, carrying out vacuum dehydration for 45min, then cooling to 70 ℃, adding 0.014g of dibutyltin bis (dodecyl sulfur) and slowly dropwise adding 10.65g of isophorone diisocyanate, reacting for 2h under the temperature condition after dropwise adding until theoretical NCO is reached, then adding 0.49g of 1, 4-butanediol and 1.71g of 1, 4-dihydroxy-2-butane sodium sulfonate, continuing to react for 4h, adding a proper amount of acetone in the reaction process to reduce viscosity, after the reaction reaches the theoretical NCO, finally adding 1.96g of hinokitiol to carry out end capping, and keeping at 80 ℃ for reaction for 1h to obtain the partially end-capped waterborne polyurethane BT-PU.
Step three, preparing Chitosan-D-rib-BT-PU
Weighing 0.34g of the water-soluble Chitosan Chitosan-lactone prepared in the first step, adding the water-soluble Chitosan Chitosan-lactone into the reaction system in the second step for a plurality of times in a small amount, simultaneously keeping the temperature at 85 ℃ for reaction for 5 hours, supplementing acetone in the reaction process to control the viscosity of the system, reducing the temperature to 45 ℃ after the reaction is finished, slowly adding a certain amount of deionized water under high-speed stirring to emulsify and disperse the system, and finally carrying out reduced pressure distillation to remove the acetone to obtain the self-antibacterial lactic acid-based waterborne polyurethane emulsion Chitosan-D-ribose-BT-PU.
Example 7 preparation of self-antibacterial lactic acid-based aqueous polyurethane emulsion Chitosan-maltose-BT-PU
Step one, preparation of Chitosan-maltose
Weighing 17.52g of chitosan, dissolving the chitosan in THF solvent containing 0.5% acetic acid, adding 51.34g of maltose after the chitosan is dissolved and clarified, stirring the mixture at room temperature for reacting for 6 hours, and then adding 3.97g of NaBH 4 And (3) continuing the reaction for 48 hours, filtering out the solid after the reaction is finished, washing with MeOH, and drying to finally obtain the water-soluble Chitosan Chitosan-maltose.
Step two, preparation of BT-PU
Weighing 20.38g of lactic acid-based polyol (hydroxyl value is 55.05mgKOH/g), heating to 100 ℃ in a reaction bottle, carrying out vacuum dehydration for 45min, then cooling to 70 ℃, adding 0.014g of dibutyltin dilaurate, slowly dropwise adding 8.06g of HDI, reacting for 2h at the temperature after dropwise adding until theoretical NCO is reached, then adding 0.49g of 1, 4-butanediol and 1.56g of 1, 2-dihydroxy-3-propanesulfonic acid sodium salt, continuing to react for 4h, adding a proper amount of acetone during the reaction process to reduce viscosity, adding 0.65g of hinokitiol after the reaction reaches the theoretical NCO, carrying out end capping, and keeping at 80 ℃ for reacting for 1h to obtain the partially end-capped waterborne polyurethane BT-PU.
Step three, preparing Chitosan-maltose-BT-PU
Weighing 2.35g of the water-soluble Chitosan Chitosan-maltose prepared in the first step, adding the water-soluble Chitosan Chitosan-maltose into the reaction system in the second step for a plurality of times in a small amount, keeping the temperature at 85 ℃ for reaction for 5 hours, adding acetone in the reaction process to control the viscosity of the system, reducing the temperature to 45 ℃ after the reaction is finished, slowly adding a certain amount of deionized water under high-speed stirring to emulsify and disperse the system, and finally carrying out reduced pressure distillation to remove the acetone to obtain the self-antibacterial lactic acid-based aqueous polyurethane emulsion Chitosan-maltose-BT-PU.
Comparative example 1
Preparation of lactic acid-based waterborne polyurethane emulsion PU
Weighing 20.05g of lactic acid-based polyol (with a hydroxyl value of 53.30mgKOH/g) into a reaction bottle, heating to 100 ℃, carrying out vacuum dehydration for 45min, then cooling to 70 ℃, adding 0.014g of dibutyltin dilaurate, slowly dropwise adding 8.06g of hexamethylene diisocyanate, reacting for 2h at the temperature after dropwise adding until theoretical NCO is reached, then adding 1.20g of 1, 4-butanediol and 2.67g of 1, 2-dihydroxy-3-propanesulfonic acid sodium salt, continuing to react for 4h, adding an appropriate amount of acetone during the reaction process to reduce viscosity, cooling to 45 ℃ after the reaction is finished, then slowly adding a certain amount of deionized water under high-speed stirring to emulsify and disperse the system, and finally carrying out reduced pressure distillation to remove the acetone, thus obtaining the lactic acid-based waterborne polyurethane emulsion PU.
Control group
The emulsion in the embodiment is prepared into an adhesive film according to the national standard (GB/T21866-2008) and is subjected to antibacterial performance test, and meanwhile, the emulsion prepared by the application number CN107236109B & lt & gt Chitosan citrate modified waterborne polyurethane and preparation method thereof & gt is used as a control group. The results are shown in the following table:
| numbering | Sterilization ratio for Escherichia coli (%) | Sterilization ratio (%) against Staphylococcus aureus |
| Example 1 | 99.6 | 99.8 |
| Example 2 | 99.8 | 99.9 |
| Example 3 | 99.7 | 99.7 |
| Example 4 | 90.3 | 91.2 |
| Example 5 | 90.0 | 90.1 |
| Example 6 | 98.5 | 98.9 |
| Example 7 | 98.7 | 98.8 |
| Comparative example 1 | 0 | 0 |
| Control group | 88.7 | 89.1 |
The data show that the lactic acid-based aqueous polyurethane emulsion prepared by introducing the aqueous chitosan and hinokitiol functional groups has excellent synergistic antibacterial property.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (6)
1. The self-antibacterial lactic acid-based waterborne polyurethane is characterized by having the following structural general formula:
wherein:
degree of polymerization n 1 1 to 20;
degree of polymerization n 2 1 to 15;
x has the following general formula:
r is any one or more of residues of 2, 4-tolyl diisocyanate, 4' -diphenyl methyl diisocyanate, isophorone diisocyanate or hexamethylene diisocyanate;
p is any one or more of residues of 1, 2-dihydroxy-3-propane sodium sulfonate, 1, 5-dihydroxy-3-pentane sodium sulfonate or 1, 4-dihydroxy-2-butane sodium sulfonate;
y is any one or more of lactose residue, maltose residue or D-ribose residue.
2. A method for producing the self-antibacterial lactic acid-based aqueous polyurethane according to claim 1, comprising the steps of:
1) dissolving chitosan in an aprotic solvent containing 0.3-0.7 wt% of acetic acid, adding a carbohydrate after the chitosan is dissolved and clarified, stirring and reacting for 4-6 h at room temperature, then adding a reducing agent to continue reacting for 24-48 h, filtering out solids after the reaction is finished, washing with MeOH, and drying the solids to obtain water-soluble chitosan, wherein the carbohydrate is selected from any one or a combination of more of lactose, maltose or D-ribose;
2) adding acetone, diisocyanate compound, lactic acid based polyol and tin catalyst into a reactor, and reacting under N 2 The method comprises the following steps of (1) carrying out protection and stirring reaction in an oil bath system at 65-70 ℃ for 1.5-2 hours, then adding a chain extender to continue the reaction for 2-4 hours, then adding hinokitiol according to the ratio of the amount of-OH added to the amount of-NCO in the system to be 1 (1.5-2.5) to carry out end capping, and carrying out reaction at 75-80 ℃ for 0.5-1 hour to obtain a partially end-capped aqueous polyurethane prepolymer;
3) adding the water-soluble chitosan obtained in the step 1) into the partially end-capped aqueous polyurethane prepolymer obtained in the step 2) for several times, simultaneously heating to 80-85 ℃ for reaction for 3-5 hours, supplementing acetone in the reaction process to control the viscosity of the system, reducing the temperature to 40-45 ℃ after the reaction is finished, slowly adding deionized water under stirring to emulsify and disperse the system, and finally carrying out reduced pressure distillation to remove the acetone, thus obtaining the self-antibacterial lactic acid-based aqueous polyurethane;
wherein:
in the step 1), the molar use ratio of the chitosan, the carbohydrate and the reducing agent is (1.5-2): 1: (2-5);
in the step 2), the molar use ratio of the diisocyanate compound, the lactic acid-based polyol and the chain extender is (1-15): 1: (0.5-3), wherein the tin catalyst accounts for 0.5-0.7 wt% of the total mass of the three;
in the step 3), the weight ratio of the water-soluble chitosan to the partially-blocked waterborne polyurethane prepolymer is (0-1): 1;
the diisocyanate compound is selected from any one or more of 2, 4-tolyl diisocyanate, 4' -diphenyl methyl diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate;
the chain extender comprises any one or more of 1, 2-dihydroxy-3-propane sodium sulfonate, 1, 5-dihydroxy-3-pentane sodium sulfonate or 1, 4-dihydroxy-2-butane sodium sulfonate, and also comprises 1, 4-butanediol.
3. The method for preparing self-antibacterial lactic acid-based aqueous polyurethane according to claim 2, characterized in that: the aprotic solvent is selected from any one or more of DCM, THF or MeCN.
4. The method for producing self-antibacterial lactic acid-based aqueous polyurethane according to claim 2, characterized in that: the reducing agent is selected from any one of sodium borohydride, sodium cyanoborohydride or sodium triacetoxyborohydride.
5. The method for preparing self-antibacterial lactic acid-based aqueous polyurethane according to claim 2, characterized in that: the tin catalyst is selected from stannous octoate, dibutyltin dilaurate, dibutyltin bis (dodecyl sulfur), dibutyltin diacetate or stannous chloride.
6. A self-antibacterial lactic acid-based waterborne polyurethane emulsion is characterized in that: the emulsion of claim 1, wherein the emulsion has a solid content of 20 to 40 wt%.
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